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Title: Connections Between the Speciation and Solubility of Ni(II) and Co(II) in Molten ZnCl2

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1];  [2];  [3];  [4];  [5];  [6];  [1];  [4];  [1];  [5];  [7];  [7];  [1];  [5]; ORCiD logo [8]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Ludwig Maximilian Univ., Munich (Germany)
  4. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Univ. of Washington, Seattle, WA (United States)
  7. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  8. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Understanding the factors that control solubility and speciation of metal ions in molten salts is key for their successful use in molten salt reactors and electrorefining. In this work we employ X-ray and optical absorption spectroscopies, and molecular dynamics simulations to investigate the coordination environment of Ni(II) in molten ZnCl2, where it is poorly soluble, and contrast it with highly soluble Co(II) over a wide temperature range. In solid NiCl2 the Ni ion is octahedrally coordinated, whereas the ZnCl2 host matrix favors tetrahedral coordination. Our experimental and computational results show that the coordination environment of Ni(II) in ZnCl2 is disordered among tetra- and penta-coordinate states. On the other hand, the local structure of dissolved Co(II) is tetrahedral and commensurate with the ZnCl2 host’s structure. The heterogeneity and concomitant large bond length disorder in the Ni case is a plausible explanation for its lower solubility in molten ZnCl2.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Molten Salts in Extreme Environments (MSEE); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725; AC07-05ID14517; FG02-97ER45623; SC0012704
OSTI ID:
1597256
Report Number(s):
BNL--213598-2020-JAAM
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 7 Vol. 124; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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